Hydrocarbon conversion process



Nov. 21, 1950 P. EVANS 2,531,356

HYDROCARBON CONVERSION PROCESS Filed Sept. 27, 1947 3 Sheets-Sheet 1 FIG-l HAQZPER 000551? HOPPER l/EA TE]? 0017 VE YORS 01L GIMME 95 SURGE CHAMBER REGYGLE WASH/N6 SOLVE/VT FRAGT/OAMTOR 12/ COMBUSTION m4 SUPPORT/N6 ASPHALT 6A5 //v INVEN TOR.

IAVY FUEL OIL OUT AGE/VT .01? ATTORNEY Nov. 21, 1950 L. P. EVANS 2,531,356

HYDROCARBON CCNVERSION PROCESS Filed Sept. 27, 1947 3 Sheets-Sheet 2 HOPPER HEAT EXCHANGE FL UIO OUT FIG. 2

HEAT EXCHANGE FLU/O IN w STEAM I RE GE NE RA T OI? ASPHALT FLUE EASPHALTING CHAMBER FINES NEIOVAL VENT l0 OOMBUST ION SUPPORTING 6A3 IN EXCHANGE)? JNVENTOR.

Lou/s P. E w; [vs

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AGENT OR ATTORNEY i atented Nov. 21 1950 UNITED STATES PATENT OFFICE 2,531,356 n'riiae'caiason coivviiasron rii'oens's Louis P. Evans, Woodbury, Ni-Ji, assignor to ;S-

(zany-Vacuum Oil Company, Incorporated, a corporation of New York' Application September 27, 1947,- Serial NoL WGA 'ZZ This invention pertains to a process for com version of high boiling hydrocarbons at controlled elevated temperatures in the presence of a par ticle-form contact mass material. This invention is particularly concerned with a process for 5 cuts as well as asphaltic constituents and a very the conversion of hydrocarbon feed-stocks which large amount of petroleum coke, the disposal of contain both asphaltic. and oily constituents. which often creates a serious refinery problem;

Such conversion processes may involve treat- A major object of this invention isthe pro-'- ins, reforming, Polymerization, oxidati esulvision of a process forconversion of high boiling p a H c et o the Y 1o asphalt bearing hydrocarbon fractions which: A p l ly p iw p fl is t e C ta yt c process avoids the above described difficultiesof cracking conversion of hydrocarbons, it being th a l-,1 well-knownfor example, that hydrocarbon frac-- Anmther object is the provision of a practical tion b lin above he line boiling range method ii orcatalytically converting the oily eon-n may be converted o lo boiling s e 11,- stituents in high boiling etroleum residuums a hydrocarbons upon being subjected to without the .foomationoi prohibitive amounts at contact with a suitable sol-id porous catalyst at 9kg during. such conversion. temperatures of the order of 800 F. and upvvards Another b ie'gt f this invention is mg v- Elmiat pressures usually abPVe 'atmospherlcsi'on of a practical continuous cyclic process for Heretofore, such conversion processes hav the catalytic cracking conversion of petroleumbeen limited to the conversion of relatively light, figm' feedi Stock? P F of the tendency of t vision or a combination petroleum res-id-uumdeasphalt contaming stocks to cause the formation agpfia-mng ana \bnvers'iofi process; of excessive deposits or coky contaminants on the s and owe? dmissof this, mvenfidfi W11} catalyst-Which deposlts carinot be economlcauy become" apparent'fi om the following discussion; f Order to avoid these heavy coke process ofthis invention is broadly one q s K rendert the P Process E whereinthe hydrocarbon-feed fraction bearing ig glgsgg ggg g gg gg f igi ifi g asphalt and oily constituents is'contacted under stocks Ewhen available with a broad boiling "3O Sufiimbllj SQTpfiQnQCQnQ-mOnSWWh a pafi'icl'aform an to a preliminary tar separation step porquslcemaict maitenadl W bl f? separate an easily vanori-zable fraction from a i im r j wi fi it i y q in h liquid fraction which bears the asphaltic con- 2p; h hl i ?W9 Y P v stituents and to subject only the vaporizable l l q n? sill lji .i9 li'l ll l fi fraction to catalytic cracking while discarding the 19 3 l pm??? ta i the liquid tar separator bottoms. Since this disl9 ,l f mi lim 9f} 99m??? carded fraction may be made up of a large proan? li l l l,q fimsi l l i l portion of valuable oily constituents and a fi1 5 1 5 9???? F air"??? r n?? smaller proportion of asphaltic constituents, it m QPWllWfPiil? hse F s? is obvious that a large quantity of otherwise aci rlllls lllfibl q in? W i ceptable catalytic cracking feed stock is lost and 35??? QKWFfPfl q 9 imi l i l unavailable as such in the prior art tar separa- It??? 9 l19 ll l l h ter i i tor operation. When the crude residuum is not l ef h a bagxltgs and natural and treated. of such boiling range and does not contain su-b- W ar PF Q P l l liquid Petroleum @3 stantial amounts of vaporizabie gas Oil it has been tlons, theasphaltic constltuents may be adsorbed considered in practice as being unsuitable as such the y and thus removed from the y for a cracking charge stock. The problem is b'-- Stituents; Such a process is commercially emcoming increasingly serious due to the fact that i e d co li f mineral?! ill relatively low boiling petroleum crudes are be-' c'dlati'onof theoilsthmu'gfi Clays-W159-adlsffifitsl coming less plentiful and the crudes which are The p p o he o po e" cf he most readily available high boiling. m p called percolation and contactfiltration-processes which the oily constituents boil so high as to pre OilI fi' th by the .p D vent their separation from asphaltic constituents it is the y cQnsfiilluefit not the p fi'fi by distillation process Without subjecting them cdnstitucnt 'soebecbv e o ac to temperatures at which undesirable thermalteria l-r This fundamentaldifference niakes pos'si cracking and excessive coking occur. Asa result, his the combination cracking process of this inin order to use such high boiling stocks at all, it vention and pe isthe elimination of the as: is necessar first to subject them to a preliinplial't materials" without contamination of the inary thermal coking step to provide some lower' catalyst thereby. It hasbeenfoundthat porous 26 Claims. (01. 196-52) boiling oily fractions for a subsequent catalytic. cracking operation.- By products from the cok-..

ing process are a heavy liquid out which may contain a substantial amount of oily constitu contact materials, having a structure corresponding to that of an inorganic oxide gel having a substantially uniform porosity of low macropore volume with an average pore diameter not exceeding about 125 angstrom units and a particle It will be apparent from the above Table I that when the gel type sorbent particles were greater than 30 mesh size that even at relatively high temperatures and long contact periods the oily constituents of low viscosity and carbon residue size preferably not smaller than about 30 mesh 5 were sorbed in the pores of the sorbent while the for most operations, have the ability to sorb the asphaltic constituents could be Washed away with oily constituents of a liquid hydrocarbon fraction a suitable washing solvent, in this case benzol. while leaving substantially unsorbed the asphal- On the other hand, in the case of sorbent partitic constituents. Natural and treated clays and cles ranging from 30-60 mesh size, when the conbauxites such as are employed in oil filtering and tact period was 24 hours (Experiment 4) or even decolorizing processes do not appear to have 2 hours (Experiment '7), the sorbent acted simithis property. The macropore volume of the lar to a normal filtering clay and preferentially contact material employed in the present invenadsorbed the asphaltic constituents. But when tion should be relatively low so that the pore 5 the contact time was reduced to two minutes volume is mostly that of micropores. In general, (Experiment 5) the 30-60 mesh sorbent exhibited the volume of macropores, that is, those ores a preference for the oily constituents over the ashaving radii larger than 100 angstrom units, phaltic constituents. When the particle size was should constitute less than about 30 per cent of reduced below 60 mesh, the sorbent preferentially the total pore volume and preferably 10 per cent adsorbed the asphaltic constituents even at very or less. The measurement of pore size and pore low contact periods (Experiment 6). size distribution in various porous materials is The effect of contact time and temperature is discussed in detail by L. C. Drake and H. L. Ritter shown in Table II below in which the deasphaltin Industrial and Engineering Chemistry, Analying results on an East Texas residuum having an tical Edition, volume 1'], pages 782-791, 1945. 25 original Saybolt Universal viscosity of 512 sec- The methods described there were essentially onds at 210 F. and a Ramsbottom carbon resihtose employed in determining the bulk densidue of 11.1. In this experiment a silica-alumina ties,..average pore diameters, and other pore gel type sorbent of 4-8 mesh size and 0.48 bulk measurements of the adsorbents employed in the density was employed. present invention.

The size of the sorbent particles employed in Table II the process of this invention is to some extent dependent upon the variables involved in any ExperimcntNo 1 2 a particular application of the process. These important variables are time of contact between the Sorption Zone Contact Time, 15m" 4 4 2 liquid asphalt bearing cha d the sorbent in 6fi gf fit gfifi f T2 192 if the sorption zone, temperature in the sorption Ramsbottorn Carbon Residue, per cent of sorbed zone, viscosity of the liquid charge, and to a lesser m extent the ratio of liquid oil to sorbent charged to the sorption zone. Increasing time of contact 40 In general it may be said that the particle and increasing temperature result i a decrease size of the sorbent material particularly in the in the efiiciency of separation of asphaltic and case of inorganic oxide gel type sorbents should oily constituents. Decreasing viscosity of the liqbe greater than about 60 mesh Tyler and preferuid charge has the same efiect. On the other ably within the range about 0.022 to 1.0 inch hand increasing temperature and decreasing vis- 5 average diameter. The best results may be obcosity both result in more rapid sorption of the tained by limiting the sorbents within the range liquid oily constituents by the sorbent. If the 0.03 to 0.20 inch average diameter and of reasonratio of sorbent to liquid charge is excessive some ably uniform size. It is pointed out, however, loss in separation efiiciency results. By proper that by proper control of the variables discussed control of these variables some latitude in the hereinabove and also of the average pore diameter average diameter of the sorbent employed may be of the sorbent, operation according to the method provided. However, when the diameter of the of this invention may be obtained on sorbent parparticles becomes too small, the sorbent preferenticles outside the size ranges given although the tially adsorbs the asphaltic constituents from results will be less satisfactory. It is contemthe liquid charge in the same manner as well plated that in its broader aspects this invention known oil filtering clays. This is shown in Table covers these latter operations as well as the I below in which is tabulated the deasphalting reoperations Within the specified preferred limits. sults obtained on mid-continent residuums using The porosity of the gel particles employed in the a silica-alumina gel type sorbent having a bulk process of this invention is of fundamental imdensity in the 4-8 mesh size range of about 0.7. portance. The degree of porosity is generally re- Table I Experiment Number 1 4 5 6 7 2 3 Charge Viscosity, s. U. v 116.9 110.9 81.8 81.8 81.8 81.8 340 Charge, Ramsbottom Carbon 2. 3 2.3 2. 3 2. 3 5.1 Mesh Size ofSorbent (Tyler) 4-8 30-60 30-60 60-80 30-00 4-8 4-8 sorption Zone Contact Time 24 hrs. 24 hrs 2 min. 2 min. 2 hrs. 72 hrs. 4 hrs. sorption Zone Temperature, F 150 150 150 150 275 Weight Ratio of Sorbent to Liquid Charge l l l l 1 l 2.2 Properties of Oily Constituents Retained by sorbent: S. U. V. 210 F. Sec. Ramsbottom Carbon, Percent 69.7 129.2 75.2 81.7 115.4 49.7 151 Properties of Materials Washed from Sorbcnt Surface: S. U. V. 210 F. Sec. Ramsbottom Carbon, Percent 164 100.1 85.9 80.5 76.0 139.2 550 flectec'd .inthe: bilikpdensitya ofg the- :gel. composite.-- I usedc; thee'lower; the bulk,'density, :the greater.-

being; the; degreeofgporosity; For the purposesof the. presentprocesa porous. sorbent particles havin .'..bu1k. densitiesotbetween aboutbxl. and 1.1

grams; neracubic; centimeter are preferred. The

bu'lkdensitiesindicat d' c rr sp n o n v e p rcdiameter otbetweeni about zoand aboutil25.

angstrom'taunits. Preferably, the sorbent used will;havetal:buikidensityqbetween; about 0.6 and i.-

abut:.;-:0:8: graln .per:cubiccentimeter... Gel. particles having; a bulk-density greater than about 0.8.have. been found to; have excellent selectivity butipoor sorbingcapacity, while particles with a bulkmdensityless than about 0.6 have relatively Door selectivity; However, since the selectivity of the. deasphalting process improves with a decrease ingtemperature, particles with a bulk density less thanqQifi would be satisfactory. for deasphalting.

stockszwhich; can; be processed at low temperatures.

Thedegrceofporosity of a synthetic inorganic oxidejigel will; in general, depend onthe condition underwhich it is prepared and allowed to set to'jgelation. A particularly-convenient method of preparing geliparticles used in the process of this in ention is; described in U. S. 2,384,945; issued September 18, l9 l5, to Milton M. Marisic. It'is there disclosedthat spheroidal particles of v in-. organic oxide gel may be prepared by mixing an acidic; stream with a stream of sodium silicate and;;allo-wing' the'resulting sol to beejected from a nozzle into arr-oilcolumn, where the gel sets inthe form of bead-like spheroids. The resulting gel spheresafter-washing, drying and tempering, were of a size varying between about 4' and about mesh. The gel beads soproduced had a buik-density of between about 0:4. and: aboutLl andan average; pore diameter of between about 205and; about 125 angstrom units. They proved tobeexcellent selective absorbents for use in the proposed this invention.

Lileewise; ,1 irregularly. shaped porous absorbent fragmentsorparticles having the structure of inorganic oxide gels may be used. However, in general, spheroidalparticlesare to be preferred, since attrition losses are then at aminimum and contamination \vith gel fines of theasphalt-bearing stock; is substantially eliminated.

In .general;-. siliceous gel particles will be used inthe process-of this invention, such as silica gel,- silica-alumina gel, silica-zirconia gel, silicathoriaget and the-like; Porous sorptive silica glasses havingastructure approaching that of a siliceous.gel likewise are contemplated for use in the process described herein, it being necessary, how-everythatthc porous glassesqemployed have an; average pore diameter less than about 125 angstrom units; and a macropore volume of less thanabout per cent of the total pore volume The sizeof the porous glass particles must also be.1caref-ully controlled so as to obtain preferv en-tial sorption of the oily constituents. Usuallyparticles of less than mesh sizearev undesir able. It, is' alsov contemplated that within the scope ofthis invention other porous materials not ofthe inorganic oxide gel composition which, have structuresapproaching that of a siliceous geland are withinthe above specified pore size and particle size limits may be employed within thezscope ofthis invention.

Typical of theporousglasses used are those.

described U1. S. -2',106, 744', issued February 1',

1938-, to Hood et: al. There it; isdisclosed thata; silica-alleali-boric oxide -glass:ofisuitablegcomposie glassinto, two-.phases; one phase is-..nichinalkal porous silica glasswhich: can; be; employed as,

porous: absorbent; separating medium in; accord;

ance withthepresent inventions.

Thednventiom mayv lie-most readily: understoodgg by reference to the? drawings. attacheck hereto oil-a WhlCIIZ Fi ure: l. is a Schematic arrangement. of the p atus; s: showngnartiallv; n. sec ion;

Eignre-iidsasimilarview0i a modified arrange ment; and,

Figure; 3 isa diagrammatic flOWwSkGtCh .015 Still;

nothenmodifieaarran cment.

All; ofthesedrawings are-highly diagnammaticz.

in form .1

urrn snow. to: Figure: 1, foraa study: ofi theg'. processor this invention;vessellllisa dcaSphaltingcha-mber whichmay be; of-arectangular onan other; desired. crossrsectionali. shape; A; pant tion: 2.4.; acrossrthe; upper; section of:chamber-- upperaendzg Tubesflfidepend from partitioni 30: fiOWLQf contact: material. from xehambeniii; .ont.

material columnmaintainedvinithei sorptiomisec tionr28; of thedeasphaltingwessel; Particleiform contacti'materialhaving a catalytic; activitmfo thr desired conversion-r and. being suitable .io sorbing theaoilyconstituents-of ,a liquidssfee while leaving; substantially. unsorbed the; asphaltr: constituents thereof is; cooled to acsuitableltemaperature; in: hopper.v 2 positioned above vessel.v 20; and then passed via conduit 2| into: vessel :20; to...

keep replenished-the; column of such material; section 2 8? offvessel- 2E9. which'ycontainszboth asphaltic and .oily: con-.

spaced; alongheaders l I.

become-sorbedzin: the portsof the contactmatee rial and the. asphalt: constituents remain;sub-.=-

stantially UI'ISOXDGCL; The; contactrmaterial bearing sorbed oily constituents. and; the unsorbedi. liquidare: withdrawn ;together from. the. bottom. of vessel 26;throughduct 22 at a, suitable rate controlled by the: valve 3i.

Themixediliquidand:solid material are directsbymeans; of drivemotor: [1.

substant-iallythe width of, belt l4; so as. to. uni:- formly distributesolid material and liquid across the belt: Suitable guards: (notshown) mayhem provided, within;- chamber 35 along the opposite: 701' sides: of .the' belt. M. to. prevent solid" particles A drain pan: l'fli is:- supported: our itsopposite' sides from the wall of chamber 35; between the pulleys I5 and-l6 andbeloivw theibelt I 4 soas. to. receive liquid whicls ..draiI1s:,therethr0ugh-.s The. drained liquid cons from: falling.v off. the sides.

qn isaprepared by afusiomprocess; Heat treat j menb ct; this; glass-1 results in separation. of: th :1

a system!oiithisdnyention inwhichsome; of the age.

the; surface of the substantiallyecompartrcontac A hydrocarbon feed-stock...

taining the asphalt constituents is withdrawn from pan it via conduit I9 to the asphalt receiver 32. Entrained solid fines may be removed from the bottom of receiver 32 by means of outlet 33 and asphalt may be withdrawn via conduit 34 to pump 36. The asphalt containing liquid then may be entirely pumped from the system via conduits 3'! and 38 or in part recycled via conduits 3? and 39 to inlet manifold feeding the deasphalting chamber. In some operations such recycling is desirable in order to reduce the amount of oily material in the finally discarded asphalt constituents to a minimum.

The contact material is carried along on belt l4 in the direction of the flow arrows and the contact material from which most of the unsorbed liquid has been separated by draining is discharged from the belt N onto the washing chamber 48. The chamber 48 communicates on its lower end with the boot section of a bucket elevator 43. In elevator 43 buckets 44 having perforated bottoms are moved upwardly and downwardly on endless chain 45 so as to transfer the washed contact material from the elevator boot section upwardly to duct 355 feeding supply hopper 46 which in turn feeds the hydrocarbon convertor 41. The bottoms of the elevator buckets M are perforated, the perforations being of such size as to retain the contact material particles while permitting liquid to pass therethrough. The elevator casing is inclined and the buckets are so shaped that liquid which drains from any given upwardly moving bucket does not fall into the bucket moving upwardly therebelow, but is delivered back to the elevator boot section. A suitable washing solvent such as a naphtha, kerosene, benzol or light gas oil fraction may be introduced from an outside source through conduit 42 into conduit 43 through which it passes into the elevator boot section. The solvent passes from the elevator boot section into the lower section of chamber 48 via passage A9 and then passes upwardly through the washing chamber to be withdrawn from the upper portion thereof through conduit 50 to a washing solvent receiver 5|. Baflles 52 provide a zig-zag passage in chamber 45 through which the contact material passes as it descends through the bath of upwardly moving washing solvent. The solid particles are in this manner subjected to a quick wash under conditions so controlled as to accomplish the removal of asphalt containing liquid adhering to the outer surfaces of the contact material particles with-- out substantial separation of the sorbed oily constituents from the contact material. A relatively small amount of washing solvent may also be sorbed by the contact material during the washing operation. The washed contact material may thus contain a substantial amount oi sorbed oily constituents from the original feed, a relatively small amount of washing solvent (and in some cases practically no washing solvent) and in some instances small amounts of asphalt constituents from the feed. It should be understood that while the gel type contact material particles of the type described have the unusual characteristic of sorbing oily constituents rather than asphalt constituents from high boiling feeds, nevertheless, in the case of some feed fractions the gel type catalyst will also sorb relatively small amounts of asphalt materials. It has been found that this relatively small amount of sorbed asphaltic materials will not increase the coke deposits on the catalyst to prohibitive levels. It should be understood that in claiming this invention in the expressions while leaving the asphalt constituents substantially unsorbed; or contact material suitable for sorbing substantially only the oily constituents of the liquid feed and in like expressions the word substantially is intended to allow for these relatively small amounts of asphalt constituents which may in some operations be sorbed along with the much larger amount of oily constituents in the contact material pores.

The washed contact material bearing sorbed oily constituents may be passed from the convertor supply hopper 46 into the upper end of convertor 41 as a substantially compact, elongated gravity feed leg flowing downwardly in conduit 55. Within the upper section of convertor 41 a horizontal partition 56 is positioned so as to define a seal chamber 57 in the upper end of the convertor. It is into this seal chamber 5'! that the contact material feed is delivered.

A suitable inert seal gas such as steam or flue gas may be introduced into seal chamber 51 at' a rate sufficient to maintain a gaseous pressure therein above that in the conversion section of vessel 4'1. Conduit I33, diaphragm valve BI and differential pressure control instrument I32 are provided for this purpose. A plurality of uniiormly spaced vertical conduits 58 serve as a passage for solid flow from seal chamber 51 onto the column 53 of contact material maintained in a lower section of the converter. A second partition 60 posit oned near and above the lower ends of conduits 58 provides a chamber 6| surrounding the conduits 58 and within the vessel 4? which chamber is sealed from the seal chamber 57 and from the column of contact material 59 by partitions 53 and 68 respectively. An inlet conduit 52 for hot regenerated contact material extends into the upper sect'on of chamber BI and an outlet conduit 63 for discharge of that contact material is connected into partition 60. A packing gland 65 is provided to permit expansion of conduit 63 through the wall of vessel 41 while preventing the escape of vapor. The partition 65 may be of such shape as to form a tapered bottom for chamber 6! so that contact material may be easily withdrawn therefrom via conduit 53. The arrangement is such that the relatively cool contact material bearing sorbed oily constituents which enters seal chamber 57 and then passes downwardly through conduits 58 may be heated by indirect heat transfer with a hot regenerated contact material which is introduced into chamber 6| through conduit 62 and withdrawn through conduit 63 at a rate controlled by valve 65. The regenerated contact material is thereby partially cooled and is transferred by means of a suitable conveyor 61 to the combined hopper and cooler 29 from which it passes into the deasphalting chamber 28 as the contact material supply thereto. The regenerated contact material in hopper 29 is cooled to a temperature suitable for its introduction into deasphalting chamber 20 by means of a suitable heat exchange flu d introduced at 58 and removed at 69. If desired, heat transfer tubes may be provided in both hoppers 29 and it; and the heat exchange fluid with drawn from the heat transfer tubes in hopper 29 via conduit 69 may be introduced into the tubes in hopper 45 through conduit 70. The heat recovered from the final cooling of the regenerated contact material may thereby be utilized for partially heating the cooler, oily constituent bearing contact material in hopper 46.

The heat exchange fluid, relieved of its heat in hopper =46 "may be withdrawn :from the tubes therein through conduit H and rintroduced into 'the tubes in hopper 29 through conduit 68. A pump I2 may -be provided to cyclically circulate the heat exchange fluid and an exchanger J3 m'ay be provided topermit any heat adjustments that may be required by the desired contact material outlet temperature from hoppers 29 and 45. Heat may'either be added or' withdrawnby meansof exchanger '53 as the particular operation'involved requires, Considering again the convertor 41,- the partially heated 'oil bearing contact material :Jinlet manliold box iiiis provided-on one side of ."the 'vessel'to supply heat exchange fluid to the tubes iiiia'nd an outlet manifold box 'li'isprovided on the opposite side of vessel 41. Heatex- .change fluid enters box isthrough inlet conduit 18 and leaves box Ti through conduit '19. Any

suitable heat exchange fluid such assuperheate'd steam, flue "gas :or'molten'metallic alloys, lead or inorganic salts, etc. may "beemp'loyed. As will be shown hereinafter a'preferablesourceof the heat is'the "contact mater arregenerator. 'After being "heated to a suitable conversion temperature the oily constituents'are catalytically converted to the "desired gaseous products "which-are withdrawn from the lower section'pf vessel 41"bymeans of :spaced rows of, inverted coll e'c'ti'ngtroughs'llfl and "853' provided withoutlet 'pip'es'fil and *8l'. fThe pipes 81 and 8 l .connect into manifolds '32 and 8'2 respectively from which the'gaseous products are withdrawn through conduits B3 .and .83 respec- 'tively 'Which'merge-into a single outlet conduit "84. 'Valves 85 and 86 are provided on :conduits 83 and 83 respectivelyto permit control'iofthe amount of the "rate "ofgas withdrawal at each level of collectorsf 'In'thelower .sectiontof vessel '41, there are provided twohorizontal, vertically lspaced' partitions wand-89. A plurality 'oiuniformly distributed tu'bestfl depend from partition' 83 and asinaller plurality of orifices 9| .are provided in partition 89. The orifices 9|. .are horizontally offset with respect to tubes 90 so asto proportionately receive streams of contact material therefrom and to cause them to merge into a smaller plurality of streams which in, turn merge .into a single outlet stream in outlet econduit 93. The arrangement-issuch'as ,to provide for uniform withdrawal ofrcontact material from all portions ofrthe horizontal'crosssectional area of vessel All through theoutlet93. .Thisarrangement is fully described vandtclairned.inUnited States application Serial Number-$73,861, .filed January 28, .1943 .in Whichithe present applicant was one of the applicants and.whichrissued as Patent No. 2,412,136 on DecemberB, 1946.

A suitable purgegasrsuch as steam or flue gas may be introduced into thelower sectionrof vessel 6'? through conduit ,i35uin order to .purge the outfiowing used contact,.materialsubstantially .ire'e of thelower boilingconversion-products.

; .-It viill-benoted thatminthe operationcdescribed thus Vfarithe .inorganicgel .,type content material particles serve r the dual tunctionof serving 23.5

United States Patent Oifice'Uune 17, $942 application Serial Number '44 7;4;-33',' 'fileda "United States Patent Oifice' Junel'i, 1 942 n which applications the present applicant-"isione an unusual sorbent permitting separationidf-asphaltic constituents from the oily constituents of the original feed fraction and also as a oa'talyst to promote 'theconversion of the oily con- 'stituents in vessel 41 once a suitable-conversion temperature has been reached.

The used contact material which is withdrawn "from vessel substantially separatelyoffithe gaseous conversion products, through conduitzfiii and throttle-valve 94 thereon has lost a sub "stantial part of'its catalytic"effectiveness due to deposition of --a carbonaceous contaminant fore, transferred "by :oonveyor -lii'r to" chute- 96 feeding the regenerator 91. A surge' cha'n'iber 98 is provided in the upperfend of regenerator 9'! to receive the used contact "material. "The regenerator shown "in Figure l is of 'the mul tiistage variety which is described and claimed-fin application Serial "Number "447;432, filed 5? 'e of the applicants,- and which issued as Patent Nos. 2,417,399 and 2,436,780;"respectivelyfin general the regenerator 9'l is divided into avertical series-of alternating "burning and cooling stages. Separate gas inlets 9,9,!00, I01 and-W112 and separate gas-outlets l 04-101 inclusive spac'ed vertically from the inlets, are provided for the burning stages. Thegas-inlets'areisuppliedfgby a combustion supporting 'gas "such as "oxygen; i or mixtures of air andflue gas, from inlet. marriiold H18. Flue gas passes :from the- 'iburnm'g stagesthrough outlets "Hit-l0! and ismanifolded'into'outlet flue I09. 'Heat'transfertubes or coils "may be suitably spaced within the cool- ;ing stages; "-Pipes I ID are inlets to these tubes andpipes "H I :are outlets :therefrom. The inlet pipes H0 connect into an ,inlet manifold :11! and'the-outlet pipes connect into anioutlet' mani- "fold I13. As pointed out hereinabovetheiexcess 'heat released 'by burning the carbonaceous contaminant from the contact material may be carriedby a suitable heatjexchange 'fluidgpassing from outlet manifold H3 through'conduit the manifold box 16 supplying. the heat transfer tubes "15 in converter "41. The ,heattexchange fluid after giving up' its heat to the contact'ma- 'terial in vessel '4'! may then pass via manifold box 11, "conduit ,19, pump H1 and conduit H58 into the -m1et manifold H2 which suppliesithe heat transfer. tubes in the ,regenerator cooling stages through pipes H0. Any excess heat Iii-b,- eratedby the contaminant burning,over that required for the final, heating of thewcontac't material and .oily constituents in convertorgfl may -beeremov.ed ,by the .evapora'tionuofswater to provide high. pressure steam. in .,'drum. 5.

Theheat exchange fluidmaytake-anyof anum her-of formszsuch as a suitable,gaswundenpres sure or fused metallic oxides .or mixtures of certain.fusedinorganicsalts.

.I-Iot regenerated contact material-is withdrawn from the lower end of'regenerator '91 through outlet 1119 at thedesired :rateas controlledby throttle valve 420. The hot regeneratedcontact material is .then transferred bye-conveyor J2! to-hopper-.I 22..from whichsit-passes-via conduit-62 into-the chamber .6! incvessel- M. was

described ,hereinabovehthe regenerated contact material ..is, -partiall=yl cooledrin ichamber i6l.;;:by indirect heat transfer with-"cooler -oil: rbeaming' -used in the deasphalting operation.

is then passed to hopper 29 where it is finally cooled to a temperature at which it may be re- It will be noted that by virtue of heat exchange between the contact material in chamber 6| and that in conduits 58 and by virtue of the exchange of the heat between the contact material in hoppers 29 and 46 as described hereinabove, a large portion of the heat removed from the hot regenerated contact material to adapt it for the deasphalting operation is recovered and used for preheating the contact material to a temperature suitable for conversion of the oily constituents. Moreover, any residual heat required for the heating of the oily constituent bearing contact -material is obtained from the contaminant combustion reaction and transferred to the contact material by a heat exchange fluid passing through heat transfer tubes I5. It will be understood that the heat thus obtained from the contaminant burning not only serves to raise the ,contact material and oil temperature in vessel 41 but also serves to supply the endothermic reaction heat required for the conversion of the oily constituents to the desired products.

Considering again the gaseous products obtained from converter 41 it is pointed out that the term gaseous as used herein in describing and in claiming this invention is intended in the sense of covering materials which are in ..the gaseous phase under the particular operating conditions involved regardless of the normal phase of those materials under atmospheric conditions. For example, gaseous conversion products leaving the converter through conduit 84 at a temperature of the order of 800 F. to 950 F. and say 10 pounds gauge pressure may exist substantially entirely in the gaseous phase under these conditions although gasoline, gas -oil and heavy fuel oil constituents may be present which are ordinarily liquids under atmospheric conditions. The gaseous conversion products are directed by conduit 84 into a fractionator I36 which may be of the type conventionally used for this purpose. A heavy cycle or fuel oil fraction may be withdrawn from the bottom of the fractionator I36 through conduit I31. The

.fuel oil may be pumped by pump I38 through conduit I39 and through exchanger I40 whereby it is cooled. The cooled fuel oil may be withdrawn from the system or it may be recycled as part of the heavy liquid hydrocarbon feed to the deasphalting chamber 26. Gasoline and light products may be withdrawn from the top of fractionator I36 through conduit I4I through which it passes to condenser I42. Part of the condensed material may be refluxed via pipes I43 and I66 and part withdrawn via pipes I43 and I44 in order to be further treated and fractionated to provide a finished gasoline product. An intermediate boiling fraction or a light cycle oil boiling, for example, within the broad range about 400 F. to 800 F. may be withdrawn from an intermediate point along the fractionator I36 via conduit I6'I. This cycle oil may be pumped by pump I45 through conduit I68 to exchanger I46 wherein it is partially cooled. All or a portion of the cycle oil may then be withdrawn from the system through conduit I41. It has been found desirable to employ at least a portion of this cycle oil as the washing solvent for washing asphaltic material from the outer surface of the contact material particles in washing chamber 40. In case of such operation the cycle oil from exchanger I46 passes via conduit 12 I48 through cooler I 49, wherein it is adjusted to a suitable temperature for the washing operation and then into the boot section of elevator 43 via conduit 48. The cycle oil may entirely replace or merely supplement washing solvent from an external source introduced via conduit 42. The used washing solvent collected in receiver 5I may be passed therefrom through conduit I56 to pump I5! and then via conduit I52 through exchangers I46 and I46 into a suit- 'able solvent fractionator I53. In exchangers I46 and I the solvent is vaporized and heated to a suitable flash temperature for introduction into the fractionator I53. In fractionator I53 the washing solvent (i. e. cycle oil) is distilled from the asphaltic and high boiling material removed from the contact material in chamber 40. The asphalt containing liquid is withdrawn from the bottom of fractionator i53 through conduit I64 and the recovered solvent vapor is Withdrawn from the top of fractionator I53 through conduit I54. The cycle oil vapors are condensed in condenser I55 and passed to pump I56. The condensate may in part be pumped through conduits I57 and I58 back to tower I53 as reflux, and part through conduits I51 and I59 to an outside storage. Alternatively part of the condensate may be passed through conduits I51 and I66 to conduit I48 to be reused as washing solvent.

Alternatively in some operations, the fractionator I53 may be eliminated and the used washing solvent containing asphaltic constituents may be withdrawn from the system through conduit I62 to be employed as a cutting stock in preparing refinery fuel blends and the like. This latter alternative is particularly feasible when a cycle gas oil is employed as the washing solvent. On the other hand, when an outside solvent such as a naphtha fraction is employed as the washing solvent, it is usually desirable to recover the solvent by fractionation.

While the system described hereinabove is one of the preferred forms of this invention, it should be understood that the various elements making up the particular combined system described are shown in highly diagrammatic form in Figure 1 and that the invention is not intended to be limited to the particular detailed construction of the various elements as shown. For example, while it is preferred to percolate the liquid charge downwardly through a column of the gel particles in the deasphalting chamber, nevertheless it is contemplated that within the scope of this invention the contacting of the gel particles and the liquid charge may be accomplished in a number of other ways and any method which permits the desired contacting is considered to be within the scope of this invention. For example, the liquid charge and the gel particles might be merely charged to a batch type mixer provided with suitable mechanical mixing devices and after suitable mixing has been accomplished, the material may then be discharged from the mixer to a suitable liquid solid separator. Likewise, other methods and apparatus than that described hereinabove may be employed to effect separation of unsorbed liquid material from the contact material bearing sorbed oily constituents. For example, a rotary type filter provided with suitable means for accomplishing both filtering off of unsorbed liquid and washing of the contact material may be employed. In some operations the washing step may be eliminated entirely and the combination of draining and purging of the contact material 'with':a"suitable purging gasimay e'be "relied'tupon :tto Tseparate :the contact material from. :unsorbed 'lii asphalt containing. liquid...i Moreover, whileI-in tthetsystem describedhereinabove the "washed icontacttmaterial -was -.partia'lly' heated and then :mhar edthrough a gravityieedilegtothe coni'verton'iit S isflcontemplated that the preliminary ii martial heating ':step may be eliminated and all :nof'zthe heating accomplished withinathe "convertor. .nlsoisuitableiiorced feed devices may beam tersubstitutedior the gravityfeed leg :in less pre- .t'ferred ".forms of the -invention 'as means of .initroducing'the' "contact material bearing fsorbed :oily constituents into the convertor. 'Itiiis also tacontemplated that the convertor and regenerator, reconstruction may; rbeLizrnateri'ally different i from .dshat shown'iin-Figure vl. Other :'suitable :means izforiremovaltof gaseous products from the con- -2YGI'SiOI1-ZOII8 may be employed where-desired and -lin '"some "operations. the contact :material and;

monversion "productsimay b'e withdrawn together z'mnd then separated. .The"iregenerator"may be :cof :rthe .single stage zitype '1:and..-:also-1;of the other 'EUYPES which will "be described hereinafter, if

zidesired. .wLSinc'e sthe inorganic "oxide? gel type 'zcontact azmaterial 'invo'lvedis preferably substantially of 530' mesh sizeand; larger: it is more practical and 'zidesirablesin order to preventiundue attrition of .-'-;";the contactwmaterial ito'ihandle'the contact ma -:t'erial as a? substantially "compact moving bed "or icolumnrin the :convertor"andregenerator and to :convey: :itEbetween vessels byf'continuous bucket FBIEVatOIS. However," Within thelbroader scope i of ethis 'iinvention .sit tisccontemplated that the con- :iitMb'b material may move insuspensionzin-asuit- :1; able :gaseous'stream -oras'ta fluidized mass with- HILiD. the :conversion and regeneration vessels and vutlrat:means other .than bucket ielevators smay be i'zzemployed .ior transferring 1 the-contact imaterial a cfrom 01161-0116 to another. :It'iS further conetemplated that within its broader. scope the method of this invention may involve a substanatially in-situ rprocess wherein the contact ma- -iterial:rem'ains permanently. :in one for more ves- .isels. For ;example,the deasphalting, draining, washing, heating conversion and catalyst regena-eration 'and cooling stepsmay beconducted in :proper cycle in a single -chamberin which the -cont'act material particlesremain as a-fixed-bed. :-.-A batch type operation wherein the contact ma- -terial is moved periodically,- batchwise from cone to zone is also contemplated. It should also be understood that within thescope ofthis .inventionit is contemplated that the contactmauterial bearing sorbed'oilyaconstituents after separation of unsorbed liquid may beheated to the temperature suitable .ior efiecting the desired conversion of theoilyconstituentseither by :in- .direct or by direct heattransfer with suitable fluid heat exchange mediumsby indirect heat .transfer fromraihot particle .-form-solid which mayor .may. not 5 be regeneratedscontact material and by the .mixing of .hot particles .of .substan- -itially inertfheatcarrying material withthe oily icons'tituent bearingcontact material.

vIt will be understood thatthe desirablecondi- ."tions or operation duringthe deasphalting,.washing, conversion and catalyst regeneration and cooling steps "will vary depending upon the par- 'version reaction involvedandthe particular conversionproducts desired. Certain .generallcon-di- 'tions of operation'must, :however, be observed. ..As regards the deasphalting operations the tempera- "tureat'which the sorption of oily constituents by ticular liquid charge stock involved and the con- -":14 :Ttheparticle formzgeltype contact-material is conv'ducted should be highcnoughto give the oil suf- 'fficient fluidity topermit rapid .sorptionof the soily constituents but low enough to permit the lzcontact .material to function selectively. The ikma'ximumitemperature maintained in the son:-

'lI'liiOIliZOIIB is dependent'on the viscosity of the "ifstock beingtre'ated. The 'sorption of oily-eons.stituents becomes less selective as the viscosity decreases. The desirable isorpti'on temperature elh'as been round'to'vary from 'below' roomtemperafiture to 'aboutiSUO" F. depending on the'liquicl naction treated. The temperatureofthe hydrocarb'on' liquid charged intothe sorption zoneiand .fl5 thecon'ta'ct material supplied thereintoishould tbe bo'th adjusted topIOVidG the desired 'sorpti'on 1 temperature. Theccontact materiahshoul'dnot be permittedl'to contact the asphalt containing liquid feed at temperature at -which 1' substantial .20 thermal cooking of'the liquid fraction-would take place. This -means 'that'tin general "the contact material should be 'cooledinthopp'er 29 of Figure 1 for example, to "a temperature which is at least 'below-about"Z-50 F. The pressure. in the son:-

ti'on aone *mayconvenientl be within ."the'order of atmospheric"to 501$ per square'inch. The residence time of the contact material withinisection 1.28 "of chamben'z t, ine; the sorptionzonefmay *vary' from about 1-10 hours depending "upon the uid fraction involved; thetemperature and the a tio of the contact'material'totheliquid charge. In many operations "it is desirable to control the residence "time of the contact material "in chamber 28 by means of valve 3! Such-as "will 35 permit substantial saturation of the-'contactma- *terialwith sorbed oil-y constituents.

The ratio of contact material to' liquid charge -tothe deasphalti-ng "chamber "may vary from "about 0.5 to"20 parts'by weight "of contact mate- 'riaT-per =-partof liquid asphaltbearing charge and preferabl irom about 2'to 6 partso'f co'ntact-material per part of liquid charge.

The amount of solvent employed in the washing operation may vary depending upon the char- "acteristics of the solvent and of the unsorbed liquid involved. In general the contact material "washing should be a relatively quick wash" so controlled as to prevent removal by the solvent ofsubstantial'amounts of sorbed oily constituents from the contact material. The amount of solventemployed may be of the order of 0.25 to 2:0 volumes of solvent per volume of contactma'terial. "In some operations the purging step following "the washing step maybe omitted but when this stepis employed'the purging gas employed should be agaswhich is not apt tocause oxidation of the oily constituents during the conversion, unless-of course, the conversion process involved is a partial oxidation process. Steam, nitrogen, "flue gas and low molecular-weight hydrocarbon gases aresuitable purging gases formost operastions.

When the contact material bearing sorbedoily .constituentsis partially heated before introduc- "tion to'jthe con-versionzone as shown in Figure.1, it should be heated only to a temperature which is substantially below the desiredconversion tempera'ture' Usually a temperature of the vorder'of ."'?50F. is the'maximum temperature to which the contact material should be heated in'hopper .of Figure .1. .As has been pointed .out, the contact material introduced to chamber 29 should be belowabout 750 'F. .so that regeneratedecori- "tact material .inhopper '29 of .Figure i-snould. .be 75 cooled to a'level at leastbelowabout750" F.

The operating conditions within the converter 41 will vary depending upon the activity of the catalyst employed, the particular petroleum charge involved, the reaction involved and the products desired. In general it has been found desirable to maintain the pressures within a range varying from sub-atmospheric to about 200 pounds per square inch. Pressures of the order of to 50 pounds per square inch gauge are preferred. The temperature for the conversion for cracking operations may vary from about 750 F. to 1100 F., temperatures of the order of 850 to 1000 F. being preferred where gasoline is the desired product. Where non-condensible gases are the principal desired product somewhat higher temperatures may be employed. The ratio of contact material to hydrocarbon throughput may vary from about 1.0 to 40 parts by Weight of contact material per part of hydrocarbon charge. In the operation of the system shown in Figure 1, the contact material bearing oily constituents may be heated to a temperature just below the desired conversion temperature by the time it discharges from conduits 58 and is then heated by means of tubes 15 to a temperature sufficiently above the desired average conversion temperature to supply the endothermic heat of hydrocarbon conversion and to insure the desired average conversion temperature. For example, contact material heated to about 400 F. in hopper 46 may be further heated to about 800 F. by the time it reaches the column 58 in convertor 4?, whereupon it may be heated by tubes 15 to about 950 F. The contact material may then cool to about 850 F. before reaching the discharge conduit 93 thereby giving an average conversion temperature of about 900 F.

In alternative operations, the heat transfer effected from chamber 6| may be sufiicient, in combination with partial preheating in hopper 46 to provide all the contact material heating required in which case the tubes 15 may be omitted.

In still another alternative operation the tubes 15 may be so spaced and positioned as to provide indirect heat transfer all along the length of the conversion zone so as to permit maintenance of the contact material substantially at the desired conversion temperature all during the conversion of the oily constituents. In a preferred form of this alternative operation the regeneration and conversion zones may themselves be positioned in intimate heat transfer relationship with each other along their lengths so as to permit heat transfer from the moving catalyst undergoing regeneration through the walls of the regeneration zone into the reaction zone. In this mannor, the heat of hydrocarbon conversion is supplied directly from the regeneration zone and the catalyst in the regeneration zone is cooled sufficiently to prevent its temperature from rising to heat damaging levels.

In the contact material regenerator, pressures of the order of atmospheric to about 100 pounds per square inch may be employed, pressures around atmospheric being preferred. The contact material temperature should be controlled below a heat damaging level by removal of heat therefrom during the course of the contaminant burning. The heat damaging level is that level at which and above which the contact material suffers permanent loss in catalytic effectiveness for the conversion involved or loss in sorptive eihciency. The heat damaging temperature may vary from temperatures above about 1150" F. to

'temperatures above about 1450 F. depending upon the particular gel type catalyst involved.

A modified system for conducting the process of this invention is shown in Figure 2. Many of the elements in Figures 1 and 2 are substantially identical and these elements bear like numerals in both drawings and need not be further discussed in detail. In the arrangement shown in Figure 2 the deasphalting, draining, washing and purging steps are all conducted within a single vessel 2%. A partition 20! across the upper section of the vesesl 200 provides in the upper end thereof a contact material surge chamber 282 into which regenerated contact material is introduced at a suitable temperature through conduit 203. A conduit 204 depending from partition 20! serves as a passageway for contact material from surge chamber 202 into sorption zone 205, and also to provide a liquid distributing space 206 above the contact material column in zone 205. High boiling liquid hydrocarbon charge containing asphaltic and oily constituents is fed through conduit 20-! into space 208 at a sufficient rate to maintain a pool of liquid therein over the surface of the contact material column. The liquid percolates downwardly through the column of downwardly moving gel type contact material particles in zone 2B5 whereby the oily constituents are sorbed and the asphalt constituents remain unsorbed. The liquid containing asphalt constituents upon reaching the lower section of zone 205 drains off from the contact material through the openings 283 in partition 209. The partition 209 is adapted to retain and direct the contact material flow from zone 205 into a central portion of the horizontal cross section of vessel 200 so as to provide between the partition and the vessel wall a liquid collecting space 2st from which solid flow is excluded. Downwardly sloping drip baffies 2H are connected along the outer side of partition 209 below the openings 203. A second bafile structure 252 which may be in the form of a hollow cylinder closed on top and bottom is positioned centrally within the passage for solid flow 2l3 defined by partition 20!] so as to cause the solid to flow through an annular passageway between the baffie structure 2l2 and partition 209. Openings 214 also adapted to permit passage of gas or liquid therethrough while preventing solid flow therethrough are provided in the vertical walls of bafile structure 2i2. A suitable purge gas such as steam or flue gas is introduced into the distributing space 2I5 provided by structure 2i3 through conduit 216. This purge gas passes horizontally across the contact material column within passage 2l3 and through the openings 288 in partition 209 thereby serving to sweep unsorbed liquid from the contact material into collecting space 2&0. The purging gas may be withdrawn from space ZIB through conduit 218 near its upper end and the drained liquid containing asphalt constituents may be withdrawn from collecting space 2l0 through conduit 2i9 near its lower end to the asphalt receiver 32. Horizontal partitions 22! and vertical foraminate baffle 22% which may be cylindrical in form provide below the draining section in vessel 200 a washing and purging section. The baflle 220 serves to define within the lower section of vessel 4'! and within the central portion of its horizontal cross-section a passage for solid flow 222, and an outer collecting space 223. Vertically spaced bafile arrangements 22 and 225, similar in construction to baflle structure 2l2 provide a washing solvent distri- .17 buting zone 226 and a purge gas distributing zone 22? respectively centrally and longitudinally disposed of the passage 222. Washing solvent is introduced into zone 226 through conduit 228 and passes horizontally across the solid column and then through the openings in partition 220 into the collecting space 223. Purge gas is introduced into zone 22'l through conduit 22-9 and then passes horizontallyacross the contact material column and through the openings in partition 22%? into the collecting space 223. Purge gas may be withdrawn from space 223 through conduit 230 near its upper end and used washing solvent containing asphaltic material maybe withdrawn from the lower section of space 223 to receiver 51 via conduit 23L By the arrangement hereinabove described the contact materialpasses as a continuous substantially compact column slowly downwardly through the sorption zone 285, then through a drain zone where unsorbed liquid i8 provided a cooling stage 232 wherein the contact material is cooled to a suitable temperature for reuse in the deasphalting operation. For this purpose heat transfer tubes (not shown) may be provided Within stage 232 and a. heat exchange fluid may be introduced thereinto through inlet conduit 2 59 andwithdrawn therefrom through outlet conduit The hot heat exchange fluid withdrawn from stage 232 may be pumped by pump through conduit 252 and exchanger 253 wherein it gives up its heat to used washing solvent pumped by pump [5! from receiver 5| through conduit 552 and through exchanger 253 into a washing solvent fractionator I53. The cooled heat exchange fluid from exchanger 253 may be further cooled by cooler 25 3 and then returned to the heat transfer tubes in cooling stage 232 via conduit 249. In this manner the ,is drained and purged therefrom, then through a washing zone wherein liquid asphaltic material adhering to the outer surfaces-of the solid particles is washed away, then through a purging zone wherein washing solvent is removed and finally is discharged from the bottom of vessel 28!} through conduit 235 at a rate controlled by throttle valve 236., The contact material bearing sorbed oily constituents is then conducted by a suitable conveyor 23? to hopper238 wherein it may be partially heated by means of a suitable heat exchange fluid introduced at 234 and removed at 239. This partial preheating step may, if desired, be omitted, The contact material then passes downwardly through gravity feed leg 55 into the upper end of convertor 240. An inert seal gas is introduced into the upper end of vessel through conduit E3!) to maintain a seal gas blanket adjacent the lower end of feed leg 55 thereby preventing the escape of hydrocarbon reactant vapors therethrough. A plurality of spaced, vertical, finned heat transfer tubes 24! are positioned between suitable headers 2t2 and 243 within an upper portion of convertor 2%. Heat exchange fluid from the cooling stages of a regenerator ill similar to the one shown in Figure 1 may be pumped by pump ll! through conduit 24d feeding inlet header 242 and thence through tubes 241 to outlet manifold 243 from which it is withdrawn through conduit 245 to steam exchanger I I5 and thence through conduit lid back to the cooling coils 2.46 in regenerator ill. Stuffing boxes 24'! and 248 are provided at the points of passage through the shell of conduits 24 i and 245 respectively. The contact material bearing sorbed oily constituents passes downwardly as a substantially compact column through convertor 249, being heated by the heat released by contaminant burning in regenerator transferred to the convertor by the heat exchange fluid passing through tubes 24!. The contact material is heated by tubes 2M to a temperature suitable for conversion of the oily constituents to the desired gaseous products. The gaseous products are withdrawn from the lower section of the convertor 2st through conduit 24! and the catalyst after being purged; by a Suitable inert gas introduced into vessel 24!) at E35 is withdrawn from the bottom of the convertor through conduit 93 at the desired rate as contrailed by throttling valve 94. The used contact material is transferred by conveyor 95 to the :7 generator 9! wherein it is regenerated in the manner discussed hereinbefore'. Below'the low crinost burning stage in regenerati l 9 there is heat recovered from cooling of the hot regenerated catalyst in stage is utilized for vaporizing and heating used washing solvent to a suitable temperature for its fractionation in frac tionator I53. The recovered solvent, separated from asphaltic constituents is removed from the top of vfractionator 853 via conduit I54 to condenser from which it passes in part through conduit I58 as reflux to the fractionator and in part through conduit 255 to pump 255 byrwhich it is pumped through conduit 228 back to the washing section of vessel 2%. Cooled regenerated contact material is withdrawn from the bottom of cooling stage 232 through conduit 35'? at a suitable rate controlled by throttle valve 258 and is transferred by conveyor 259 back to conduit 2533 supplying the vessel 209 In another modification of this invention the oily constituent bearing catalyst may be heated by mixing it with a hot inert heat carrying material which has previously been heated in the catalyst regenerator. Such a system is shown in Figure 3. In Figure 3, the liquid feed fraction introduced at 26%} and the regenerated catalyst introduced at 25! are contacted in deasphalting chamberQBZ. The catalyst bearing sorbed oily constituents and the unsorbed liquid pass from chamber 252 via conduit 253 to drain chamber 28% wherein the liquid is drained off, being withdrawn at 265. The catalyst then passes via conduit 266 to washing chamber 26? wherein it is washed by vsuitable washing solvent introduced at 35!. The used washing solvent is withdrawn at 258. The washed catalyst passes from chamber2$8 via conduit 269 to conveyor. 2w by which it is transferred to hopper 2?! wherein it may be heated somewhat by heat exchange fluid introduced at 212 and withdrawn at 273. II" desired, the catalyst may pass directly from hopper 2TH, without heating through gravity feed leg 2% to the seal chamber 275. The catalyst then passes from seal chamber H5 through conduit 276 at a suitable rate controlled by valve ET! into the upper section of convertor 218. Within the upper section of the convertor there is provided an arrangement of baflles adapted to cause the thorough mixing of the catalyst stream entering via conduit tit and of a stream of particle-form hot inert heat carryingmaterial entering through conduit 23% from a second [seal chamber 28!. The mixing device consists of averticahhollow cylinder 282 open on either end supported by rods Z'liicentrally of the vessel cross-section and surrounding the lower end of inert material inlet cenduit 28s. Asmaller cylindrical shield 233 is constituents.

19 nular passage 285 for catalyst flow. Catalyst is directed into the annular passage from conduit 2115. Hot heat carrying material particles pass into the space enclosed by shield 283 and are caused to flow around a small centrally placed bafiie 286 positioned directly below the outlet of conduit 288. The inert solids stream from under shield 283 mixes with the catalyst stream from annular passage 285 and the combined streams flow onto a conical bafiie 281 by which they are further mixed and then pass onto an accumulation of the mixed solids in a basin 288. The basin 288, supported by rods 330, is of smaller diameter than the vessel 218 but is of such diameter and so positioned with respect to the lower end of the cylindrical baffle 282 as to prevent the overflow of solids over the edge of the basin 2%. The mixed contact material is distributed onto the surface 295 of the column of mixed material in the vessel therebelow by means of the spaced apart basin drain tubes 289. The rates of catalyst introduction and inert solids introduction into the convertor are controlled by valves 211 and 291 on conduits 215 and 281} respectively in such a manner as to accomplish the heating of the catalyst bearing sorbed oily constituents to a suitable conversion temperature for the oily The gaseous conversion products are withdrawn from the lower section of convertor through outlet 292 and the mixed spent catalyst and heat carrying material after being purged by a suitable purge gas entering the vessel at 293 are withdrawn from the bottom of vessel 218 through conduit 295. The rate of solid material withdrawal is controlled by valve 296 on conduit 295. The mixed solids are then transferred by conveyor 291' to the regenerator 298. The mixed solids pass downwardly through regenerator 298 being contacted with air introduced into the lower section of vessel 298 through conduit 299. Flue gas resulting from the burning off of the carbonaceous contaminants from the solid particles is withdrawn from the upper section of the regenerator through conduit 300. The excess heat released by the contaminant combustion is absorbed as increased sensible heat by the solid heat carrying particles thereby preventing overheating of the catalyst without the requirement for heat transfer tubes within the regenerator. The hot regenerated catalyst and hot inert heat carrying material are withdrawn together from the regenerator 288 through conduit 3G1 and then separated in a suitable separator such as a mechanical screen 3 12. The separated catalyst passes via conduit 3114 to cooler 395 wherein it is cooled to a suitable temperature for reuse in the deasphalting operation by means of a heat exchange fluid introduced at 3116 and withdrawn at 301. If desired, heat transfer tubes within cooler 3135 may be dispensed with and the cooling may be accomplished by passing a cold gas such as air directlv through the bed of catalyst in cooler 365. The cooled catalyst passes from cooler 38 5 through conduit 31l8to conveyor 3119 by which it is transferred to deasphalting chamber 262. The hot inert heat carrying ma terial separated from the catalyst by screen 302 passes via conduit 315 to. conveyor 318 by which it is transferred to the hopper and exchanger 311, In exchanger 311 the temperature of the inert, material may be upwardly or downwardly ad--: justed by hot or cold gas introduced to exchanger X 311 at 318, depending upon the thermal requirements of the system. The heat exchange gas is withdrawn from exchanger and hopper 311' through conduit 314. The hot inert heat carrying material then passes downwardly through gravity feed leg 319 to seal chamber 281 from which it is introduced to the convertor 218 via conduit 289. An inert seal gas such as steam or flue gas is introduced from conduit 32;) to seal chambers 215 and 281 via conduits 321 and 322 respectively at a rate so controlled by diaphragm operated valve 323 and differential pressure control instrument 324 as to maintain an inert gaseous pressure in seal chambers 215 and 281 slightly above that in the upper section of convertor 218. For example, the pressure in seal chambers 215 and 281 may be maintained about to 1 pound per square inch above that in the upper section of convertor 218 thereby preventing escape of reactants through the solid feed system.

In order to permit the separation of hot regenerated catalyst from the inert heat carrying particles the heat carrying material should consist of particles either smaller or larger in diameter than the catalyst or of a substantially different density or both. For example, where a 4 to 16 mesh siliceous gel spherical (bead) catalyst is employed, the inert heat carrying particles may be of the order of 0.3 to 0.5 inch average diameter or of the order of .01 to .05 inch average diameter. The system shown in Figure 3 has the advantage of permitting the use of very simple and economical regenerator construction and of permitting the elimination of heat transfer tubes in both the regenerator and reactor. Where the heat carrying material is of substantially different density than the catalyst, it may be separated therefrom by a suitable conventional method and apparatus adapted for separating solids of different densities. The system may be very easily and economically maintained in thermal balance by means of direct heat transfer between the inert solid material and a suitable gas in exchanger and hopper 311. If the heat balance conditions in the system require addition of heat to the system this may be easily accomplished either by the introduction of a heated gas into the direct contact exchanger 311 through conduit 318 or by the introduction of air and a suitable fuel gas which may be burned in the bed of inert material within exchanger 311.

In an alternative form of operation the hot inert material may be separated from the used catalyst discharged from convertor 218, recycled directly to combined hopper and exchanger 311, heated therein either by hot gases or by burning a fuel gas, and passed back to the convertor. In

such an operation the regenerator may be provided with heat transfer tubes in order to permit control of the catalyst temperature during the contaminant burning.

As an example of the result obtainable by the method of this invention the treatment of an East Texas crude bottoms fraction having an A. P, I. gravity of 15.0 at 60 F., a Saybolt Universal viscosity of 512 seconds at 210 F., a pour point above F., and a Conradson carbon residue of 11.1 percent may be considered. The vacuum assay distillation of this feed fraction was as follows:

T. I. B. P 880 10% 964 30% 1026 40% 1054 47% 1082 This feed fraction was contacted in a suitable is confined chamber with a silica-alumina, spheroidal gel catalyst prepared by the method described in United States Patent 2,384,946 issued September 18, 1945 to Milton lvlarisic. The catalyst unpacked density was about 44 pounds per cubic foot and consisted of particles falling within the range 4 to 16 mesh by Tyler Standard Screen Analysis. The catalyst has been regenerated until the residual carbon thereon was below 0.5% by weight. During the operation the temperature was maintained at about 75 F. and the pressure was substantially atmospheric. The ratio of liquid to catalyst charge to the sorption zone was about 3.2 parts by weight of catalyst per part by weight of liquid charge. The residence time within the sorption zone was about 240 minutes. The unsorbed liquid was recycled until substantially all of the oily constituents had been removed therefrom. Finally a tar fraction amounting to about 30 percent by weight of the liquid charge was separated from the catalyst bearing sorbed oily constituents and the catalyst was washed with about half of its weight of Stoddard Solvent, the residence time of the catalyst in the washing operation being limited to about 3 minutes. The catalyst after washing contained about 22 percent of its original weight of sorbed oily constituents which represented about 70 percent by weight of the original liquid charge. The catalyst bearing oily constituents was then heated to a temperature suitable for the cracking conversion of the sorbed oily constituents in a confined conversion zone. An analysis of the sorbed oily constituents before conversion was as follows:

.A. P. I. gravity 17.1; viscosity (kiln) at 210 F.- 46; pour point above 120 F., and Conr'adson carbon residue 5.7% by weight.

The conditions in the conversion zone were as follows:

Average ttmperature--890 F. Pressure ii /in. gauge Residence time10 minutes The following conversion yields were obtained:

Gasoline (410 F. E.P.)-41% by weight of the sorbed oily constituents Cycle oil-44% by weight of the sorbed oily constituents Coke on catalystl0% by weight of sorbed oily constituents Gas5% by weight of sorbed oily constituents The coke deposited on the used catalyst was about 2.6% be weight of the catalyst and was readily removed by burning at temperatures within the range 800 F. to 1100 F.

In the above described example a light cycle stock of 32 A. P. I. gravity and boiling within the range about 400 F. to 675 F. by A. s. 'r. M. distillation was substituted for the Stoddard Solvent in the Washing step without any material change in the washing and final conversion results.

It should be understood that the details of apparatus construction and arrangement, of operating conditions, and of applications of the process of this invention given hereinabove are intended merely as illustrative and it is not intended that the scope of this invention should be limited thereto or limited otherwise except as it may be limited in the following claims.

This application is a cohtinuation-in-part of applicat'on Serial Number 720,271 filed in the United States Patent Oflloe January 4, 1947, now

abandoned.

- I claim: r 1. A method for conversion of a'sphalt contraining liquid hydrocarbon feeds at elevated temperatures which comprises: contacting the asphalt containing feed with a porous particleform contact material having the structure of an inorganic oxide gel, in which the total macropore volume is less than about '30 per cent of the total pore volume and in which the particles are substantially all larger than about '30 mesh, at a temperature below about 500 'F., whereby the oily constituents of said feed are sorbed in the pores of said contact material while the asphalt constituents remain substantially unsorbed; eifecting a substantial separation of the contact material bearing sorbed oily constituents from the unsorbed material and heating said contact material to a temperature suitable for the desired conversion of said oily constituents.

2. A process for the conversion of the high boiling oily constituents present in high boiling petroleum feed fractions containing asphaltic and oily constituents to lower boiling gaseous gasoline containing products which comprises: subjecting the feed fraction in a confined zone to contact with a porous inorganic oxide gel-type contact material consisting of particles having a greater average diameter than about .022 inch and having less than 30 per cent of its pore volume taken up by macropores, the remaining pore volume being taken up by smaller pores, at a temperature below about 500 F., whereby the oily constituents of said feed fraction are substantially sorbed by said contact material and the asphalt constituents remain substantially unsorbed, effecting a substantial separation of unsorbed liquid from said contact material hearing sorbed oily constituents, passing said contact material downwardly through a confined conversion zone as a substantially compact column while heating it to a temperature above about 750 F. which is suitable for conversion of said oily constituents to gaseous gasoline containing products, withdrawing said gaseous products from the lower section of said conversion zone, withdrawing used contact material bearing carbonaceous contaminant deposits from the lower end of said conversion zone substantially separately of said gaseous products, passing said used contact material through a confined regeneration zone while maintaining its temperature above the minimum level required for rapid burning of said deposits but below a heat damaging level, passing a combustion supporting gas into contact with said contact material in said regeneration zone to burn said deposits, withdrawing the regenerated contact material from said regeneration zone, cooling said contact material to a suitable temperature below about 750 F. and reusing at least a portion of said contact material for contacting petroleum feed fraction as aforesaid.

3. A process for conversion of the oily constituents in high boiling liquid hydrocarbon feeds containing asphaltic constituents to gaseous, gasoline containing products which comprises: maintaining within a confined deasphalting zone a substantially compact column of contact material in the from of spheroidal siliceous gel particles characterized in that it consists substantially entirely of spheroidal contact material particles having an average diameter greater than about .022 inch and having less than 30 per cent of its pore volume devoted to macropo'res, the remaining pore volume being devoted to smaller pores, distributing said liquid feed ontofsaid colui'nnadjacent-its u er end and 23 causing said liquid to pass downwardly within said column, while maintaining the temperature of said column below about 500 F., whereby oily constituents of said feed are sorbed by said contact material and the asphaltic constituents remain substantially unsorbed, withdrawing the contact material and unsorbed liquid from said deasphalting zone, draining the liquid from said contact material, subjecting the contact material to a quick wash with a suitable hydrocarbon solvent to wash from its outer surface adhering asphalt containing liquid, subjecting the washed contact material to purging With a suitable nonoxidizing purge gas to remove adhering wash solvent from the outer surface of the contact material particles, passing the purged contact material into a confined zone and heating it therein to a temperature above about 750 F. which is suitable for conversion of the sorbed oily constituents to gaseous gasoline containing products, maintaining said oily constituents in contact with said heated contact material a sulficient time to effect said conversion, effecting separation of said gaseous products from the used contact material upon which a carbonaceous contaminant has been deposited during said conversion, contacting the contact material at suitable elevated regeneration temperatures with a combustion supporting gas to burn on said contaminant deposit, cooling the contact material to a temperature suitable for introduction into said deasphalting zone and passing the cooled contact material into the upper section of said deasphalting zone to replenish said column therein.

p 4. A process for conversion of the high boiling oily constituents in asphalt bearing hydrocarbon liquid feeds to lower boiling products which comprises: contacting said liquid feed for a suitable time and at a suitable temperature with a porous particle-form inorganic oxide gel-type contact material, in which most of the pores are micropores and the volume of macropores is less than about 30 per cent of the total pore volume and in which the particles are greater than about 30 mesh size, to effect the sorption of the oily constituents of said feed in the pores of said contact material while leaving the asphalt constituents substantially unsorbed, effecting a substantial separation of the unsorbed liquid from the contact material which bears the sorbed oily constituents, and heating said contact material in a confined zone by indirect heat transfer to a temperature suitable for converting said oily constituents to lower boiling products, maintaining the oily constituents in contact with the heated contact material for sufficient time to effect said con version and effecting separation of the resulting lower boiling products from said contact material.

5. A process for conversion of the high boiling oily constituents in asphalt bearing hydrocarbon liquid feeds to lower boiling products which comprises: contacting said liquid feed for a suitable time and at a suitable temperature with a porous particle-form inorganic oxide gel-type contact material, in which most of the pores are micropores and the volume of macropores is less than about 30 per cent of the total pore volume and in which the particles are greater than about 60 mesh size, to effect the sorption of the oily constituents of said feed in the pores of said contact material while leaving the asphalt constituents substantially unsorbed; effecting a substantial separation; of the unsorbed liquid from the contact material which bears the sorbed oily constituents; subjecting said contact material bearing sorbed oily constituents to indirect heat transfer from a heated particle-form solid material to heat said contact material and th oily constituents to a temperature suitable for the conversion of said oily constituents to lower boiling gaseous products; maintaining the heated oily constituents in contact with said heated contact material for sufficient time to effect said conversion; and effecting separation of said gaseous products from said contact material.

6. A process for conversion of the oily constituents present in a liquid hydrocarbon feed containing both oily and asphaltic constituents at elevated temperatures which process comprises the steps: contacting said liquid feed in a confined zone with a porous particle-form inorganic oxide gel-type contact material, in which most of the pores are micropores and the volume of macropores is less than about 30 per cent of the total pore volume controlling the relative relationship of particle size, and contacting period and temperature to effect the sorption of the oily constituents of said feed in the pores of said contact material while leaving the asphalt constituents substantially unsorbed, the size of the particles employed being larger for longer contact periods and higher contact temperature; effecting a substantial separation of the unsorbed liquid from the contact material which bears the sorbed oily constituents; and mixing sufiicient heated substantially inert particle-form solid heat carrying material with the separated contact material bearing the sorbed oily constituents to heat said contact material to a temperature suitable for effecting the desired conversion of said oily constituents.

'7. A process for conversion of the oily constituents present in a liquid hydrocarbon feed containing both oily and asphaltic constituents at elevated temperatures which process comprises the steps: contacting said liquid feed in a confined zone with a porous particle-form inorganic oxide gel-type contact material of greater particle size than about 60 mesh Tyler, in which most of the pores are micropores and the volume of macropores is less than about 30 per cent of the total pore volume, controfling the relationships of contacting time and temperature and contact material average particle diameter to effeet the sorption of the oily constituents of said feed in the pores of said contact material while leaving the asphalt constituents substantially unsorbed, effecting a substantial separation of the unsorbed liquid from the contact material which bears the sorbed oily constituents, passing said contact material bearing sorbed oily constituents through a confined conversion zone to efiect conversion of said oily constituents to lower boiling products, effecting separation of said lower boiling products from the used contact material upon which a carbonaceous contaminant has been deposited during said conversion, passing the used contact material through a confined regeneration zone and contacting it therein with a combustion supporting gas to burn off said contaminant and cfiecting the transfer by indirect heat transfer of a sufiicient portion of the excess heat liberated by burning said contaminant in said regeneration zone to said conversion zone to heat the oily constituents bearing contact material passing therethrough to a temperature suitable for efiecting said conversion of said oil constituents.

8. A process for conversion of the oily constituents present in a liquid hydrocarbon feed stock containing both oily and asphaltic constituents at elevated temperatures in the presence of a particle-form contact mass material which process comprises: contacting the liquid. charging stock in a confined deasphalting zone with a particle-form porous contact material having the pore structure of an inorganicoxide gel in which the total pore volume is takenup mostly by micropores, there being less than about 30 per cent macropores, the contact material beingmade up substantially of particles larger than about 30 mesh size, controlling the temperature during the contacting at a level suitable for the sorption of oily constituents in the'pores of the contact material and below that which would cause substantial coking of the asphalt constituents, which con.- stituents remain substantially. unsorbed in the pores of said contact material, removing contact material and unsorbed liquid from the deasphalting zone and drawing off the unsorbed liquid, washing the contact material with a suitable hydrocarbon solvent to remove asphalt containing liquid adhering to the outer surface of the solid particles, passing the washed contact material bearing sorbed. oily constituents through a confined conversion zone while heating it to a temperature suitable for conversion of said oily constituents to valuable lower boiling products, separating said lower boiling products from the used contact material upon which a carbonaceous contaminant has been deposited during said conversion, passing the used contact material through a confined regeneration zone while controlling its temperature at a level suitable for rapid burning of said contaminant but below a level which would cause substantial permanent heat damage to said contact material, passing a combustion supporting gas into contact with said contact material in said regeneration. zone to burn on said contaminant, withdrawing regenerated contact material from said regeneration zone, passing the used washing solvent from washing said contact material from said deasphalting zone in indirect heat transfer relationship with said regenerated contact material to help cool the contact material to a temperature suitable for its use in contacting liquid asphalt bearing hydrocarbon feeds as aforesaid and to heat said solvent to a suitable distillation temperature, and

passing the heated solvent to a suitable distillation zone to efiect the separation of solvent from the asphaltic materials washed from the contact material.

9. A process for conversion of the oily constituents present in a liquid hydrocarbon feed stock containing both oily and asphaltic constituents at elevated temperatures in the presence of a particle-form contact mass material which process comprises: contacting the liquid-charging stock in a confined deasphalting zone with a particleform porous contact material having the pore structure of an inorganic oxide gel in which the total pore volume is taken up mostly by micropores, there being less than about 30 per cent macropores, the contact material being made up substantially of particles larger than about 30 mesh size, controlling the temperature during the contacting at a level suitable for the sorption of oily constituents in the pores of the contact material and below that which would cause substantial coking of the asphalt constituents, which constituents remain substantially unsorbed in the pores of said contact material, removing the contact material and unsorbed liquid from the deasphalting zone and drawing off the unsorbed liquid, washing the contact material with a suitable hydrocarbon solvent to remove asphalt containing liquid adhering to the outer surface of the solid particles, heating the washed contact material to a temperature substantially above the temperature of the washing but below about 750 F., passing the heated contact material downwardly as a substantially compact column through a confined conversion zone whilefurther heating it therein to a temperature suitable for effecting the conversion of said sorbed oily constituents to lower boiling gaseous products, maintaining the oily constituents within said conversion zone for a sufficient time to effect said conversion, withdrawing said gaseous products from thelower section of said conversion zone and sub stantially separately withdrawing the used contact material.

it. A process for conversion of the oily constituents present ina liquid hydrocarbon feed stock containing both oily and asphaltic constituents at elevated temperatures in the presence. of a particle-form contact mass material which process comprises: contacting the liquid charging stool; in a confined deasphalting zone with a par,- ticle-iorm porous contact material having the pore structure of an inorganic oxide gel in which the total pore volume is taken up mostly by micropores, there being less than about 30 per cent macropores, the contact material being made up substantially of particles larger than about 30 mesh size; controlling the temperature during the contacting at a level suitable for the sorption of oily constituents in the pores of the contact material: and below that which would cause substantial coking of the asphalt constituents, which constituents remain substantially unsorbed in the'pores of said contact material; effecting separation of the contact material bearing sorbed oilyv constituents from the unsorbed confined substantially vertical conversion zone to effect conversion of said oily constituents to lower boiling gaseous products; withdrawing gaseous products near the lower end of said conversion zone; withdrawing used contact material from the lower end of said conversion zone substantially separately of said conversion products the used contact material'having deposited thereon a carbonaceous contaminant; passing the used contact material through a confined regeneration zone; passing a combustion supporting gas into contact with said contact material in said regeneration zone to burn said contaminant; withdrawing hot regenerated contact material from said regeneration zone; passing said hot regenerated contact material in indirect heat transfer relationship with an upper portion of said column of oily constituents bearing contact material in the upper section of said conversion zone to cool said regenerated contact material and to partially heat said oily constituent bearing contact material; passing the cooled regenerated contact material to said deasphalting zone as the supply thereto; passing a fluid heat exchange medium in indirect heat transfer relationship with said contact material in said regeneration zone to control the contact material temperature below a heat damaging level; and passing at least part or the heat exchangefiuid from the regeneration zone in indirect heat transfer relationship with the column of contact material in said conversion zone below that portion of the column devoted to indirect heat transfer with hot regenerated contact material so as to further heat said oily constituent bearing contact material to a temperature suitable for efiecting said conversion of said oily constituents.

11. A process for conversion of the oily constituents present in a liquid hydrocarbon feed stock containing both oily and asphaltic constituents at elevated temperatures in the presence of a partiole-form contact mass material which process comprises: contacting the liquid charging stock in a confined deasphalting zone with a particleform porous contact material having the pore structure of an inorganic oxide gel in'which the total pore volume is taken up mostly by micropores, there being less than about per cent macropores, the contact material being made up substantially of particles larger than about 30 mesh size, controlling the temperature during the contacting at a level suitable for the sorption of oily constituents in the pores of the contact material and below that which would cause substantial coking of the asphalt constituents, which constituents remain substantially unsorbed in the pores of said contact material, removing the contact material and unsorbed liquid from the deasphalting zone and drawing ofi the unsorbed liquid, washing the contact material with a suitable hydrocarbon solvent to remove asphalt containing liquid adhering to the outer surface of the solid particles, passing the washed contact material through a partial heating zone, passing the partially heated contact material as a substantially compact column through a, confined conversion zone and heating it thereinto a temperature suitable for effecting conversion of said oily constituents to gaseous hydrocarbon products, separating the gaseous products from the used contact material upon which a carbonaceous contaminant has been deposited during said conversion, passing the used contact material through a confined regeneration zone while controlling its temperature at a level suitable for rapid burning of said contaminant but below a level which would cause substantial permanent heat damage to said contact material, passing a combustion supporting gas into contact with said contact material in said regeneration zone to burn off said contaminant, withdrawing hot regenerated contact material from said regeneration zone, cyclically passing a suitable heat exchange fluid in indirect heat transfer relationship with said hot regenerated contact material to cool the same to a temperature suitable for its introduction into said deasphalting zone and in indirect heat transfer relationship with the washed contact material in said partial heating zone to partially heat said washed contact material.

12. A process for conversion of the oily constituents present in a liquid hydrocarbon feed stock containing both oily and asphaltic constituents at elevated temperatures in the presence of a particle-form contact mass material which process comprises: contacting the liquid charging stock in a confined deasphalting zone with a particle-form porous contact material having the pore structure of an inorganic oxide gel in which the total pore volume is taken up mostly by micropores, there being less than about 30 per cent macropores, the contact material being made up substantially of particles larger than about mesh size, controlling the temperature during the contacting at a level suitable for the sorption of oily constituents in the pores of the contact material and below that which would cause substantial coking of the asphalt constituents, which constituents remain substantially unsorbed in the pores of said contact material, removing the contact material and unsorbed liquid from the deasphalting zone and drawing on the unsorbed liquid, washing the contact material with a cycle oil boiling above the boiling range of motor gasoline to remove asphalt containing liquid adhering to the outer surface of the solid particles, passing the washed contact material bearing sorbed oily constituents downwardly through a confined conversion zone as a substantially compact column while heating it to a temperature suitable for effecting conversion of said oily constituents to gaseous gasoline containing products, withdrawing the contact material from the lower section of said conversion zone, withdrawing said gaseous products from said conversion zone separately of said contact material, subjecting said gaseous products to fractionation to separate light and heavy cycle oils boiling above motor gasoline from the other products, and utilizing at least a portion of said light cycle oil for washing the contact material from said deasphalting zone as aforesaid.

13. A process for conversion of the oily constituents present in a liquid hydrocarbon feed containing both oily and asphaltic constituents at elevated temperatures which process comprises the steps: contactin said liquid feed in a confined zone for a suitable time and at a suitable temperature with a porous particle-form inorganic oxide gel-type contact material, in which most of the pores are micropores and the volume of macropores is less than about 30 per cent of the total pore volume and in which the particles are greater than about 60 mesh size, to effect the sorption of the oily constituents of said feed in the pores of said contact material while leaving the asphalt constituents substantially unsorbed, effecting a substantial separation or" the unsorbed liquid from the contact material which bears the sorbed oily constituents; passing said contact material bearing sorbed oily constituents through a confined conversion zone in admixture with a sufficient amount of hot, substantially inert, particle-form solid heat carrying material to heat said contact material and the oily constituents to a temperature suitable for accomplishing the conversion of said oily constituents to lower boiling products, said inert solid material consisting of particles of substantially different size than said contact material; efiecting a separation of said lower boiling hydrocarbon products from the mixed contact material and inert solid heat carrying material; passing the mixed inert solid material and said used contact material which bears a carbonaceous contaminant deposit through a confined regeneration zone; passing an oxygen containing gas into contact with said contact material in said regeneration zone to burn off said contaminant withdrawing hot regenerated contact material and the inert solid heat carrying material from said regeneration zone; separating the hot inert solid heat carrying material from the regenerated contact material; reusing hot heat carrying material for admixture with said oily bearing contact material for passage through said conversion zone as aforesaid; cooling the regenerated contact material to a temperature suitable for contacting said liquid feed and reusing the cooled contact material for contacting the asphalt and oily constituent bearing liquid feed in said confined zone as aforesaid.

14. The continuous cyclic process for conver sion of the oily constituents in high boiling liquid petroleum fractions bearing asphalt and oily constituents to lower boiling gasoline containing products in the presence of a particle-form catalyst which process comprises: introducing said liquid feed fraction into a confined deasphalting zone to contact at a temperature below about 509 F. a particle-form porous inorganic oxide gel catalyst made up of particles having an average diameter greater than about .622 inch, in which the pore volume is taken up mostly by micropores and the amount of the total pore space which is taken up by macropores being less than 30 per cent by volume, whereby the oily constituents of said liquid feed fraction are sorbed in pores of said catalyst and the asphalt constituents remain substantially unsorbed, effecting a substantial separation of the unsorbed asphalt constituents from the catalyst bearing sorbed oily constituents, passing the separated catalyst bearing sorbed oily constituents onto an accumulation of said catalyst in a confined seal zone, passing a stream of said catalyst from said seal zone downwardly into the upper section of a confined, elongated conversion zone, mixing the cata lyst in the upper section of said conversion zone with a stream of hot inert solid heat carrying material in such proportions as to heat the catalyst to a temperature suitable for effecting conversion of said sorbed oily constituents to lower boiling gaseous, gasoline containing products, passing the mixed contact material and inert heat carrying material downwardly through a lower section of said conversion zone as a sub stantially compact column to effect said conversion of said oily constituents, withdrawing said gaseous products from the lower section of said conversion zone, withdrawing the mixed used catalyst and heat carrying material from the lower section of said conversion zone substantially independently of said gaseous products, the cata lyst now having a carbonaceous contaminant deposited thereon, passing the mixed used catalyst and heat carrying material through a confined regeneration zone while contacting it with an oxygen containing gas to burn the contaminant from said catalyst, the heat carrying material serving to absorb the excess heat released by the contaminant burning so as to prevent the catalyst temperature from rising to a heat damaging level, effecting the separation of the hot heat carrying material from the hot regenerated catalyst, cooling the regenerated catalyst and returning it to said deasphalting zone as the catalyst supply thereto, passing the separated hot heat carrying material onto an accumulation thereof in a confined seal zone, passing a stream of said hot heat carrying material from said seal zone into the upper section of said conversion zone to mix with said oily constituent bearing catalyst as aforesaid, and maintaining an inert gaseous pressure in both of said seal zones above the gaseous pressure in the upper section of said conversion zone.

15. A process for conversion of oily constituents present in liquid fractions containing oily and asphalt constituents t elevated temperatures which comprises: sorbing said oily constituents from the liquid hydrocarbon fraction onto a por- 30 ous siliceous gel contact material in the form of spheroidal particles having average diameters within the range .022 to 1.0 inch and characterized by a substantial absence of macropores, whereby oily constituents from said liquid fraction are sorbed and asphalt constituents remain substantially unsorbed, eifecting a substantial separation of unsorbed asphalt constituents from the contact material bearing sorbed oily constituents and heating the separated contact material bearing sorbed oily constituents to a temperature suitable for effecting the desired conversion of said oily constituents.

16. A process for obtaining gasoline containing products from high boiling asphalt bearing hydrocarbon feeds which comprises, contacting said liquid feed with a solid inorganic sorbent material in which the pores are mostly micropores and the volume of pores having radii greater than about angstrom units is less than about 30 percent of the total pore volume, controlling the relative relationships of contact time, temperature, and sorbent particle size to eifect sorption of the oily constituents of said feed into the pores of the sorbent while leaving substantially unsorbed the asphalt constituents, the size of particles employed being larger for longer contact periods and higher contact temperatures, separating the sorbent bearing oily constituents from the unsorbed asphalt constituents and heating said sorbent to a temperature suitable for the desired-conversion of said oily constituents.

17. A process for conversion of oily constituents in asphalt bearing hydrocarbon liquid feeds which comprises, contacting the hydrocarbon fraction with a porous solid inorganic contact material having most of its pore volume devoted to micropores and having less than about 30 percent by volume of its pore volume devoted to pores of greater than about 100 angstrom unit radius and made up of particles of greater size than about 60 mesh Tyler until the oily constituents of said fraction are sorbed into the sorbent pores and the asphalt constituents are left substantially unsorbed, effecting substantial separation of the sorbent material bearing sorbed oily constituents from the unsorbed asphalt constituents, heating the sorbent material and sorbed oily constituents to a temperature suitable for the desired conversion of said oily constituents, and separating the conversion products from the sorbent material.

18. A process for conversion of high boiling liquid asphalt containing hydrocarbon fractions to lower boiling products which comprises, contacting said liquid fraction for a suitable time and at a suitable temperature for oily constituent sorption with a porous inorganic oxide contact material of greater particle size than about 60 mesh Tyler in which most of the pores are micropores and the volume of macropores is less than about 30 percent of the total pore volume while leaving substantially unsorbed the asphalt constituents, efiecting a substantial separation of the unsorbed liquid from the contact material which bears the sorbed oily constituents, passing the separated contact material through a confined zone while heating it therein to a temperature suitable for effecting the conversion of said oily constituents to lower boiling products, effecting a substantial separation of said lower boiling products from the used contact material which bears a carbonaceous contaminant deposit, effecting the removal of said contaminant deposit from the contact material and reusing 31 the contact material after removal of said contaminant deposit for contacting liquid asphalt bearing fraction as aforesaid.

19. A process for obtaining gasoline containing products from high boiling asphalt bearing hydrocarbon feeds which comprises, contacting Y said liquid feed with a solid inorganic sorbent material in which the pores are mostly micropores and the volume of pores having radii greater than about 100 angstrom units is less than about 30 percent of the total pore volume, controlling the relative relationships of contact time, temperature, and sorbent particle size to effect sorption of the oily constituents of said feed into the pores of the sorbent while leaving substantially unsorbed the asphalt constituents, the size of particles employed being larger for longer contact periods and higher contact temperatures, separating the sorbent bearing oily constituents from the unsorbed asphalt constituents, and passing a suitable heat exchange fluid in indirect heat transfer relationship with the sorbent bearing sorbed oily constituents to heat said sorbent and said oily constituents to a temperature suitable for efiecting the desired conversion of said oily constituents.

20. A process for conversion of oily constituents in asphalt bearing hydrocarbon fractions which comprises, contacting the hydrocarbon fraction with a porous. inorganic oxide solid sorbent made up of particles of greater than about 60 mesh Tyler particle size and having most of its pore volume devoted to micropores and having less than about 30 percent by volume of its pores devoted to pores of greater than about 100 angstrom unit radius to effect sorption of liquid hydrocarbons onto said sorbent under controlled contacting conditions, washing asphaltic constituents off of said sorbent and heating said sorbent bearing oily constituents but free of at least most of the asphaltic constituents to a temperature suitable for the desired conversion of said oily constituents.

LOUIS P. EVANS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Numcer Name Date 226,001 Riebeck Mar. 30, 1880 1,278,023 Rosenbaum Sept. 3, 1918 1,447,297 Day Mar. 6, 1923 1,568,018 Forrest et al. Dec. 29, 1925 2,188,007 Kistler Jan. 23, 1940 2,354,355 Abrams et al. July 25, 1944 2,382,755 Tyson Aug. 14, 1945 2,487,795 Evans Nov. 15, 1949 OTHER REFERENCES Allibone Journal of the Institute of Petroleum, vol. 27, pages 94-108 (1941).

A New Type of Silica Gel; by Holmes et 211., Industrial & Eng. Chem., vol. 17, No. 3, pages 280-287.

Certificate of Correction Patent No. 2,531,356 November 21, 1950 LOUIS P. EVANS It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 3, line 17, for the, Word ores read pores; line 27, for htose read those; column 14, line 20, for cooking read coking; column 24, lines 7 0 and 71 and column 26, line 62, for constituents read constituent;

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of May, A. D. 1951.

THOMAS F. MURPHY,

Assistant Oommz'ssz'oner of Patents. 

1. A METHOD FOR CONVERSION OF ASPHALT CONTAINING LIQUID HYDROCARBON FEEDS AT ELEVATED TEMPERATURES WHICH COMPRISES: CONTACTING THE ASPHALT CONTAINING FEED WITH A POROUS PARTICLEFORM CONTACT MATERIAL HAVING THE STRUCTURE OF AN INORGANIC OXIDE GEL, IN WHICH THE TOTAL MACROPORE VOLUME IS LESS THAN ABOUT 30 PER CENT OF THE TOTAL PORE VOLUME AND IN WHICH THE PARTICLES ARE SUBSTANTIALLY ALL LARGER THAN ABOUT 30 MESH, AT A TEMPERATURE BELOW ABOUT 500*F., WHEREBY THE OILY CONSTITUENTS OF SAID FEED ARE SORBED IN THE PORES OF SAID CONTACT MATERIAL WHILE THE ASPHALT CONSTITUENTS REMAIN SUBSTANTIALLY UNSORBED; EFFECTING A SUBSTANTIAL SEPARATION OF THE CONTACT MATERIAL BEARING SORBED OILY CONSTITUENTS FROM THE UNSORBED MATERIAL AND HEATING SAID CONTACT MATERIAL TO A TEMPERATURE SUITABLE FOR THE DESIRED CONVERSION OF SAID OILY CONSTITUENTS. 